Excitonic effects on infrared vibrational and Raman spectroscopy from first principles (2412.16439v1)

Abstract: We develop a first-principles approach to compute infrared (IR) vibrational absorption and Raman scattering spectra with excitonic effects included. Our method is based on a perturbative expansion of electron-phonon and electron-light couplings in the time-dependent adiabatic GW (TD-aGW) theory. We show that excitonic effects in the IR absorption spectrum can be included by replacing the free electron-hole propagators in the perturbative expression for independent particles with their interacting counterparts, which are readily available from standard GW-Bethe-Salpeter equation calculations. For Raman spectrum, our derived expression agrees with the single and double resonance terms from a diagrammatic approach. We show significant excitonic enhancement in both the IR and resonance Raman scattering intensity for monolayer MoS2, WS2, and WSe2. Moreover, the exciton-phonon coupling strength and exciton energy landscape can be accessed by analyzing resonance Raman spectrum of these materials.